CN115722233B - Regeneration method for inactivated acetylene hydrochlorination catalyst - Google Patents
Regeneration method for inactivated acetylene hydrochlorination catalyst Download PDFInfo
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- CN115722233B CN115722233B CN202211578389.9A CN202211578389A CN115722233B CN 115722233 B CN115722233 B CN 115722233B CN 202211578389 A CN202211578389 A CN 202211578389A CN 115722233 B CN115722233 B CN 115722233B
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Abstract
The invention discloses a regeneration method for an acetylene-hydrochlorination-based catalyst after deactivation, and belongs to the field of chemical industry. The regeneration of the acetylene hydrochlorination catalyst is realized by a method of combining the washing with a polar solvent and a nonpolar solvent under the ultrasonic condition and the microwave heating under the inert gas protection condition. The method has the advantages of short treatment process and good regeneration effect, can realize the recycling of the deactivated gold-based catalyst, reduce the loss of noble metal, reduce the production cost and have obvious economic and social benefits.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a regeneration method of an acetylene hydrochlorination-based catalyst after deactivation.
Background
Under the condition of the international mercury convention, the industry for producing polyvinyl chloride by using the calcium carbide acetylene method faces the greatest test, namely, the transformation from a mercury catalyst to a mercury-free catalyst in the catalytic reaction process is realized. At present, the active component research of noble metal mercury-free catalysts mainly comprises noble metals such as platinum, palladium and Jin Liao. Although these catalysts exhibit good catalytic activity and selectivity, the use of noble metals increases the cost of catalyst production and is not ideally stable and is prone to deactivation in a short period of time. In order to reduce the production cost, reduce the national strategic reserve resource loss and improve the utilization rate of noble metals, a regeneration method technology of the deactivated gold-based catalyst, which has the advantages of feasible process, strong activity regeneration capability, lower regeneration cost and no secondary pollution, is developed, and has important significance for reducing the production and operation costs.
The main reason for the deactivation of the acetylene hydrochlorination catalyst is that acetylene or a product vinyl chloride monomer is subjected to self-polymerization reaction, and the active site of the catalyst is deposited by self-polymers or covered by carbon deposition to cause the deactivation;
at present, the method for regenerating the deactivated gold-based catalyst in the prior art comprises the following steps: (1) the high temperature regeneration method is that the deactivated gold-based catalyst is placed in a furnace for high temperature roasting to remove the carbon deposition component blocked in the pores of the carrier active carbon, and the method can not effectively remove a large amount of carbon deposition in the pores and expose the catalytic active sites; (2) the gaseous oxidation regeneration method adopts oxidizing gases such as oxygen, nitric oxide, nitrogen dioxide, chlorine, hydrogen chloride and the like to activate and deactivate gold-based catalysts in the hydrochlorination process of acetylene, oxidizes elemental gold, recovers catalytic efficiency, and excessively oxidizes active groups covered on the surface of the active carbon, so that the adsorption capacity of active component gold is reduced, and a large amount of carbon deposit in pores cannot be removed very effectively; (3) the aqua regia regenerating process adopts boiling aqua regia to treat deactivated gold-base catalyst to restore its catalytic activity, and the aqua regia treatment may reverse partial gold into liquid phase to reduce gold load and produce great amount of refractory acid waste water with serious corrosion to equipment.
The invention provides a regeneration method of an inactivated gold-based catalyst, which has simple flow and good treatment effect.
Disclosure of Invention
The invention aims to overcome the defects and provide a regeneration method for solving the problem of deactivated acetylene-hydrochlorination-based catalyst.
1. A method for regenerating an acetylene hydrochlorination-based catalyst after deactivation, characterized in that the method comprises the following steps:
s1, placing the gold-based catalyst with lost catalytic activity into a polar solvent for washing under ultrasonic conditions, and performing solid-liquid separation after ultrasonic washing to obtain an S1 semi-finished product.
S2, adding the semi-finished product obtained in the step S1 into a nonpolar solvent, washing under an ultrasonic condition, and performing solid-liquid separation after ultrasonic washing to obtain an S2 semi-finished product;
s3, placing the semi-finished product obtained in the step S2 into a microwave distillation furnace, introducing nitrogen for microwave distillation treatment, and drying until the water content is less than 0.3%, thereby obtaining the regenerated catalyst.
The polar solvent is one or more of alcohols, esters and carboxylic acids.
Furthermore, the volume ratio of the addition amount of the polar solvent to the semi-finished product obtained by the S1 is 1-1.5:1, the washing temperature is 10-40 ℃, the ultrasonic frequency is 30-100kHz, and the ultrasonic washing time is 0.1-8h.
Further, the nonpolar solvent is one or more solvents selected from cyclohexane, carbon disulfide, benzene, and tetrachloromethane.
Furthermore, the volume ratio of the addition amount of the nonpolar solvent to the semi-finished product obtained by the S2 is 1-2:1, the washing temperature is 10-40 ℃, the ultrasonic frequency is 30-100kHz, and the ultrasonic washing time is 0.1-8h.
Further, the output frequency of microwaves is 1-100GHz, the distillation temperature is controlled to be 200-900 ℃ by cooling circulating water, the microwave heating time is controlled to be 1-8h, nitrogen is continuously introduced to naturally cool to room temperature, and the regenerated gold-based catalyst for hydrochlorination of acetylene is obtained.
Compared with the prior art, the invention has the following technical effects:
1. the invention adopts a chemical organic solvent treatment method to dissolve and wash the self-polymerized organic matters existing on the surface and in the pores of the deactivated gold-based catalyst, such as organic matters of vinyl chloride, dichloroethane, trichloroethane, cyclohexane, tetrachlorobutane and the like, and the solvent A and the solvent B can dissolve and wash the self-polymerized organic matters in the deactivated gold-based catalyst to recover and expand the specific surface area and the pore diameter of the carrier activated carbon;
2. the ultrasonic washing and activating process adopted by the invention has the following characteristics: (1) the solvent entering the pores of the activated carbon generates high-energy cavitation bubbles under the action of ultrasonic waves, cavitation phenomenon is generated, the cavitation bubbles are continuously grown in the solvent and burst into small bubbles, and the generated high-pressure shock waves act on the surface of the adsorption material, so that organic matters are effectively removed through thermal decomposition and oxidation; (2) the ultrasonic wave is a physical mechanical wave, the energy consumption and the cost of the ultrasonic wave are lower than those of the electromagnetic wave, the mechanical vibration effect is more obvious, the mechanical action of the ultrasonic wave can promote the emulsification of liquid, the liquefaction of gel and the dispersion of solid, and a large number of small bubbles can be generated when the ultrasonic wave acts on the liquid. The liquid is locally pulled to form negative pressure, and the gas originally dissolved in the liquid is supersaturated by the reduction of the pressure, so that the gas escapes from the liquid and becomes small bubbles. In addition, the high tensile stress of ultrasound can "tear" the liquid into a void. Therefore, the self-polymers on the surface and in the activated carbon are removed, so that the porous structure and the specific surface area are obviously increased, the regeneration of the deactivated gold-based catalyst is realized, the materials are in a static state in the ultrasonic process, and the mechanical abrasion is reduced;
3. the method adopts a nitrogen distillation method, reduces the influence of air oxidation of the surface groups of the carrier active carbon in the distillation process, and can volatilize the residual low-boiling-point organic carbon in the pores in the distillation process to recover and expand the specific surface area and the pore diameter of the carrier active carbon;
4. the invention adopts microwave heating technology, which is electromagnetic wave with frequency in 0.3-300GHz, belongs to internal heating mode, directly acts on medium molecules to convert into heat energy, and transmits to make the inside and outside of the medium heated at the same time, without heat conduction, thus achieving uniform heating in short time. The microwave heating is uniform, so that the problem of cold center in the traditional heating mode is avoided;
5. the regenerated gold-based catalyst maintains the integrity and the recycling property of catalyst particles, has large specific surface area, developed pores, strong adsorption capacity, small loss of active carbon and low energy consumption, and reduces the regeneration cost of the catalyst.
8. From the aspect of sustainable development, development of a regeneration method technology of an inactivated gold-based catalyst, which has the advantages of feasible process, strong activity regeneration capability, low regeneration cost and no secondary pollution, is particularly urgent to improve the value of recycling the inactivated gold-based catalyst.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1
The regeneration method of the inactivated acetylene-hydrochlorination-based catalyst comprises the following steps:
s1, under the ultrasonic condition, putting a gold-based catalyst (the catalytic conversion rate of a foreground converter is less than 70%) which is subjected to industrial application and catalytic activity losing into a methanol solution for washing, wherein the volume ratio of the methanol addition amount to the gold-based catalyst which is subjected to catalytic activity losing is 1:1, the washing temperature is 25 ℃, the ultrasonic frequency is 35kHz, the ultrasonic washing time is 4 hours, and the S1 semi-finished product is obtained through solid-liquid separation.
S2, adding cyclohexane into the S1 semi-finished product, washing under ultrasonic conditions, wherein the volume ratio of the addition amount of the cyclohexane to the semi-finished product obtained by the S2 is 1:1, the washing temperature is 10 ℃, the ultrasonic frequency is 35kHz, the ultrasonic washing time is 0.5h, and the S2 semi-finished product is obtained through solid-liquid separation;
s3, placing the semi-finished product obtained in the step S2 into a microwave distillation furnace, introducing nitrogen to carry out microwave distillation treatment, controlling the microwave output frequency at 20GHz, controlling the distillation temperature at 300 ℃ by using cooling circulating water, controlling the microwave heating time at 5h, continuously introducing nitrogen to naturally cool to room temperature, and drying until the water content is less than 0.3%, thereby obtaining the regenerated catalyst.
The gold-based catalyst regenerated by the method is used for synthesizing acetylene and hydrogen chloride, and the space flow rate of the acetylene is 25h -1 The molecular ratio of acetylene to hydrogen chloride is 1:1.15, and the catalytic conversion is 99.4% when the reaction temperature is 150 ℃.
Example 2
The regeneration method of the inactivated acetylene-hydrochlorination-based catalyst comprises the following steps:
s1, under the ultrasonic condition, putting a gold-based catalyst (the catalytic conversion rate of a foreground converter is less than 70%) which is subjected to industrial application and catalytic activity losing into an ethyl acetate solution for washing, wherein the volume ratio of the addition of the ethyl acetate to the semi-finished product obtained by the S1 is 1.3:1, the washing temperature is 15 ℃, the ultrasonic frequency is 55kHz, the ultrasonic washing time is 1h, and the S1 semi-finished product is obtained through solid-liquid separation;
s2, washing the semi-finished product S1 by adding cyclohexane under an ultrasonic condition, wherein the volume ratio of the addition amount of carbon disulfide to the semi-finished product S1 is 1.3:1, the washing temperature is 15 ℃, the ultrasonic frequency is 55kHz, the ultrasonic washing time is 1h, and the S2 semi-finished product is obtained through solid-liquid separation;
s3, placing the semi-finished product obtained in the step S2 into a microwave distillation furnace, introducing nitrogen to carry out microwave distillation treatment, controlling the microwave output frequency at 35GHz, controlling the distillation temperature at 400 ℃ by using cooling circulating water, controlling the microwave heating time at 3h, continuously introducing nitrogen to naturally cool to room temperature, and drying until the water content is less than 0.3%, thereby obtaining the acetylene hydrochlorination regenerated gold-based catalyst.
The gold-based catalyst regenerated by the method is used for synthesizing acetylene and hydrogen chloride, and the space flow rate of the acetylene is 25h -1 The molecular ratio of acetylene to hydrogen chloride is 1:1.5, and the catalytic conversion is 99.2% when the reaction temperature is 150 ℃.
Example 3
The regeneration method of the inactivated acetylene-hydrochlorination-based catalyst comprises the following steps:
s1, under the ultrasonic condition, putting a gold-based catalyst (the catalytic conversion rate of a foreground converter is less than 70%) which is subjected to industrial application and catalytic activity losing into an acetic acid solution for washing, wherein the volume ratio of the added amount of acetic acid to the semi-finished product obtained by the S1 is 1.3:1, the washing temperature is 15 ℃, the ultrasonic frequency is 55kHz, the ultrasonic washing time is 1h, and the S1 semi-finished product is obtained through solid-liquid separation.
S2, adding cyclohexane into the semi-finished product of S1, washing under ultrasonic conditions, wherein the volume ratio of the addition amount of acetic acid to the semi-finished product obtained by S1 is 1.5:1, the washing temperature is 30 ℃, the ultrasonic frequency is 35kHz, the ultrasonic washing time is 2h, and the S2 semi-finished product is obtained through solid-liquid separation.
S3, placing the semi-finished product obtained in the step S2 into a microwave distillation furnace, controlling the distillation temperature at 500 ℃ by using cooling circulating water with the microwave output frequency at 50GHz, controlling the microwave heating time at 2h, continuously introducing nitrogen to naturally cool to room temperature, and drying until the water content is less than 0.3%, thereby obtaining the acetylene hydrochlorination regenerated gold-based catalyst.
The gold-based catalyst regenerated by the method is used for synthesizing acetylene and hydrogen chloride, and the space flow rate of the acetylene is 25h -1 The molecular ratio of acetylene to hydrogen chloride is 1:1.5, and the catalytic conversion is 99.5% when the reaction temperature is 150 ℃.
Example 4
The regeneration method of the inactivated acetylene-hydrochlorination-based catalyst comprises the following steps:
s1, under the ultrasonic condition, putting a gold-based catalyst (the catalytic conversion rate of a foreground converter is less than 70%) which is subjected to industrial application and catalytic activity losing into a mixed solution of acetic acid and ethanol for washing, wherein the volume ratio of the added amount of the mixed solution of acetic acid and ethanol to the semi-finished product obtained by S1 is 1.3:1, the washing temperature is 25 ℃, the ultrasonic frequency is 50kHz, the ultrasonic washing time is 2 hours, and the S1 semi-finished product is obtained through solid-liquid separation.
S2, adding cyclohexane and tetrachloromethane into the semi-finished product of S1, washing under ultrasonic conditions, wherein the volume ratio of the addition amount of acetic acid to the semi-finished product obtained by S1 is 1.3:1, the washing temperature is 30 ℃, the ultrasonic frequency is 40kHz, the ultrasonic washing time is 3 hours, and the S2 semi-finished product is obtained through solid-liquid separation.
S3, placing the semi-finished product obtained in the step S2 into a microwave distillation furnace, controlling the distillation temperature at 450 ℃ by using cooling circulating water, controlling the microwave heating time to be 2 hours, continuously introducing nitrogen to naturally cool to room temperature, and drying until the water content is less than 0.3%, thereby obtaining the acetylene hydrochlorination regenerated gold-based catalyst.
The gold-based catalyst regenerated by the method is used for synthesizing acetylene and hydrogen chloride, and the space flow rate of the acetylene is 27h -1 The catalytic conversion was determined to be 99.6% at a molecular ratio of acetylene to hydrogen chloride of 1:1.5 and a reaction temperature of 145 ℃.
Claims (1)
1. A method for regenerating an acetylene hydrochlorination-based catalyst after deactivation, characterized in that the method comprises the following steps:
s1, putting a gold-based catalyst with lost catalytic activity into a polar solvent, washing under an ultrasonic condition, and performing solid-liquid separation after ultrasonic washing to obtain an S1 semi-finished product;
the polar solvent is one or more than two solvents selected from methanol, ethanol, ethyl acetate and acetic acid;
the volume ratio of the addition amount of the polar solvent to the semi-finished product obtained by the S1 is 1-1.5:1, the washing temperature is 10-40 ℃, the ultrasonic frequency is 30-100kHz, and the ultrasonic washing time is 1-8 hours;
s2, adding the semi-finished product obtained in the step S1 into a nonpolar solvent, washing under an ultrasonic condition, and performing solid-liquid separation after ultrasonic washing to obtain an S2 semi-finished product;
the nonpolar solvent is one or more than two solvents of cyclohexane, carbon disulfide, benzene and tetrachloromethane;
the volume ratio of the addition amount of the nonpolar solvent to the semi-finished product obtained by the S2 is 1-2:1, the washing temperature is 10-40 ℃, the ultrasonic frequency is 30-100kHz, and the ultrasonic washing time is 0.5-8h;
s3, placing the semi-finished product obtained in the step S2 into a microwave distillation furnace, introducing nitrogen to carry out microwave distillation treatment, controlling the output frequency of microwaves at 20-100GHz, controlling the distillation temperature to 200-900 ℃ by using cooling circulating water, controlling the microwave heating time to 1-8h, continuously introducing nitrogen to naturally cool to room temperature, and drying until the moisture is less than 0.3%, thus obtaining the regenerated catalyst.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132270A (en) * | 1990-08-30 | 1992-07-21 | Huels Aktiengesellschaft | Ultrasound method of reactivating deactivated hydrogenation catalyts |
| CN101584989A (en) * | 2009-07-13 | 2009-11-25 | 北京化工大学 | A kind of renovation process of catalyst for preparing low carbon olefin hydrocarbon by methanol |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN104549490A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for recycling and reusing waste hydrocracking catalyst through ultrasonication |
| CN104588132A (en) * | 2013-10-30 | 2015-05-06 | 华东理工大学 | Regeneration method of mercury-free catalyst (UDH) for acetylene hydrochlorination |
| CN112823938A (en) * | 2019-11-20 | 2021-05-21 | 神华科技发展有限责任公司 | Recycling method of denitration catalyst |
| CN113019469A (en) * | 2019-12-25 | 2021-06-25 | 中国石油天然气股份有限公司 | Regeneration method of deactivated molecular sieve catalyst |
-
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- 2022-12-09 CN CN202211578389.9A patent/CN115722233B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132270A (en) * | 1990-08-30 | 1992-07-21 | Huels Aktiengesellschaft | Ultrasound method of reactivating deactivated hydrogenation catalyts |
| CN101584989A (en) * | 2009-07-13 | 2009-11-25 | 北京化工大学 | A kind of renovation process of catalyst for preparing low carbon olefin hydrocarbon by methanol |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN104549490A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for recycling and reusing waste hydrocracking catalyst through ultrasonication |
| CN104588132A (en) * | 2013-10-30 | 2015-05-06 | 华东理工大学 | Regeneration method of mercury-free catalyst (UDH) for acetylene hydrochlorination |
| CN112823938A (en) * | 2019-11-20 | 2021-05-21 | 神华科技发展有限责任公司 | Recycling method of denitration catalyst |
| CN113019469A (en) * | 2019-12-25 | 2021-06-25 | 中国石油天然气股份有限公司 | Regeneration method of deactivated molecular sieve catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 李砚咸.《涂附磨具》.中国原子能出版社,2019,215. * |
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